Metal thin-film precursor composition, method of forming thin film using metal thin-film precursor composition, and semiconductor substrate fabricated using method

Abstract

Disclosed are a metal thin film precursor composition, a method of forming a thin film using the metal thin film precursor composition, and a semiconductor substrate fabricated using the method. The metal thin film precursor composition includes a metal thin film precursor compound and a growth regulator including a predetermined terminal group and structure. In a thin film deposition process, by using the metal thin film precursor composition, side reactions may be suppressed and thin film growth rate may be controlled appropriately. Since process by-products in a thin film are removed, even when the thin film is formed on a substrate having a complicated structure, step coverage and the thickness uniformity and resistivity characteristics of the thin film may be greatly improved. In addition, corrosion or deterioration may be prevented, and the crystallinity of the thin film may be improved, thereby improving the electrical properties of the thin film.

1 . A metal thin film precursor composition, comprising a thin film precursor compound; and a growth regulator,
 wherein the thin film precursor compound comprises a compound represented by Chemical Formula 1 below, and the growth regulator is a straight-chain, branched, cyclic, or aromatic compound represented by Chemical Formula 2 below.
   M x N n L m ,  [Chemical Formula 1]
 
   wherein x is an integer from 1 to 3; M is selected from the group consisting of Li, Be, C, P, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Te, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Th, Pa, U, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, TI, Pb, Bi, Pt, At, and Tn; n is an integer from 0 to 8; N is F, Cl, Br, or I or a ligand consisting of a combination of two or more selected from the group consisting of F, Cl, Br, and I; m is an integer from 0 to 5; and L is H, C, N, O, P, or S or a ligand consisting of a combination of two or more selected from the group consisting of H, C, N, O, and P.
   A n B m X o Y i Z j ,  [Chemical Formula 2]
 
   wherein A is carbon, silicon, nitrogen, phosphorus, or sulfur; B is hydrogen, an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms, or an alkoxy having 1 to 10 carbon atoms; X comprises one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); Y and Z independently comprise one or more selected from the group consisting of oxygen, nitrogen, sulfur, and fluorine and are different from each other; n is an integer from 1 to 15; o is an integer greater than or equal to 1; m is 0 to 2n+1; and i and j are integers from 0 to 3.   
     
     
         2 . The metal thin film precursor composition according to  claim 1 , wherein, in Chemical Formula 1, n is an integer from 1 to 6. 
     
     
         3 . The metal thin film precursor composition according to  claim 1 , wherein, in Chemical Formula 1, N is F, Cl, or Br or a ligand consisting of a combination of two or more selected from the group consisting of F, Cl, and Br. 
     
     
         4 . The metal thin film precursor composition according to  claim 1 , wherein the growth regulator is Cl, Br, or I or has a halide terminal group consisting of a combination of two or more selected from the group consisting of Cl, Br, and I. 
     
     
         5 . The metal thin film precursor composition according to  claim 1 , comprising one or more selected from compounds represented by Chemical Formulas 40 to 60 below. 
       
         
           
           
               
               
           
         
         wherein, in Chemical Formulas 40 to 60, a line is a bond; carbon is located at a point where bonds meet without indicating a separate element; and the number of hydrogen atoms satisfying a valence of the carbon is omitted. 
       
     
     
         6 . The metal thin film precursor composition according to  claim 1 , wherein the metal thin film precursor composition is used in an atomic layer deposition (ALD) process, a plasma atomic layer deposition (PEALD) process, a chemical vapor deposition (CVD) process, or a plasma chemical vapor deposition (PECVD) process. 
     
     
         7 . A method of forming a thin film, comprising injecting the metal thin film precursor composition according to  claim 1  into a chamber and adsorbing the metal thin film precursor composition on a surface of a loaded substrate. 
     
     
         8 . The method according to  claim 7 , comprising:
 i) vaporizing a growth regulator and adsorbing the growth regulator on a surface of a substrate loaded in a chamber;   ii) performing first purging of an inside of the chamber using a purge gas;   iii) vaporizing a thin film precursor compound in the chamber and adsorbing the thin film precursor compound on a surface area different from the surface area of the substrate on which the growth regulator is adsorbed or bonding the thin film precursor compound to a terminal of the growth regulator adsorbed on the substrate;   iv) performing second purging of the inside of the chamber using a purge gas;   v) supplying a reaction gas into the chamber; and   vi) performing third purging of the inside of the chamber using a purge gas.   
     
     
         9 . The method according to  claim 7 , comprising:
 i-1) vaporizing a thin film precursor compound and adsorbing the thin film precursor compound on a surface area of the substrate loaded in the chamber, wherein the surface area is different from the surface area of the substrate on which the growth regulator is adsorbed, or bonding the thin film precursor compound to a terminal of the growth regulator adsorbed on the substrate;   ii) performing first purging of an inside of the chamber using a purge gas;   v) supplying a reaction gas into the chamber; and   vi-1) performing additional purging of the inside of the chamber using a purge gas.   
     
     
         10 . The method according to  claim 7 , comprising:
 i-2) vaporizing a thin film precursor compound and adsorbing the thin film precursor compound on a surface of a substrate loaded in a chamber;   ii) performing first purging of an inside of the chamber using a purge gas;   iii) vaporizing a growth regulator in the chamber and adsorbing the growth regulator on a surface area different from the surface area of the substrate on which the thin film precursor compound is adsorbed or bonding the growth regulator to a terminal of the thin film precursor compound adsorbed on the substrate;   iv) performing second purging of the inside of the chamber using a purge gas;   v) supplying a reaction gas into the chamber; and   vi) performing third purging of the inside of the chamber using a purge gas.   
     
     
         11 . The method according to  claim 7 , wherein the metal thin film precursor composition is transferred into an ALD chamber, a CVD chamber, a PEALD chamber, or a PECVD chamber by a VFC method, a DLI method, or an LDS method. 
     
     
         12 . The method according to  claim 7 , wherein the reaction gas is a reducing agent, a nitrifying agent, or an oxidizing agent. 
     
     
         13 . The method according to  claim 7 , wherein deposition temperature is 50 to 700° C. 
     
     
         14 . The method according to  claim 7 , wherein the thin film is an oxide film, a nitride film, or a metal film. 
     
     
         15 . The method according to  claim 7 , wherein the thin film comprises a multilayer structure consisting of two or three layers. 
     
     
         16 . A semiconductor substrate fabricated using the method according to  claim 7 .